JPS6367481B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to catalysts for use in the polymerization of ethylene or the copolymerization of ethylene with other α-olefins. More specifically, the solid catalyst is prepared by reacting a specific organometallic compound with a titanium compound and a zirconium compound in the presence of a solid component obtained by the reaction of a specific organomagnesium compound with a specific halide, and a specific organometallic compound. Ethylene polymerization or ethylene polymerization consisting of the catalytic reactants of
This relates to a catalyst for α-olefin copolymerization. Polyolefins such as polyethylene are produced by polymerizing α-olefins using a catalyst (so-called Ziegler catalyst) consisting of a transition metal and an organometallic compound. Industrially, this is carried out by suspension polymerization, solution polymerization, or gas phase polymerization using a Ziegler catalyst. However, conventional Ziegler catalysts, such as catalysts made of titanium trichloride and diethylaluminium chloride, have low catalytic activity;
There is a large amount of catalyst residue in the polymer, which causes the polymer to become colored and deteriorate due to heat and oxidation. For this reason, industrially, it has been necessary to purify the polymer through a complicated catalyst residue removal process. The current trend is to shift to energy-saving, compact processes that increase catalyst activity and omit the catalyst residue removal process. Highly active catalysts include, for example, catalysts consisting of a magnesium compound supported on a titanium compound and an organometallic compound (Japanese Patent Publication No. 13050/1983, Japanese Patent Publication No. 13050/1986, Japanese Patent Publication No. 47/1986)
No. 1060, Special Publication No. 1973-33568, Special Publication No. 1977-34092
), catalysts consisting of a solid obtained by reducing a transition metal compound with an organomagnesium complex and an organometallic compound (Special Publication No. 52-36788, Japanese Patent Publication No. 52-36790, Japanese Patent Publication No. 52-1972)
-36791, Japanese Patent Publication No. 52-36796), a catalyst consisting of an organometallic compound and a solid obtained by reacting a transition metal compound with a reaction product of an organomagnesium complex and a halogenating agent (Japanese Patent Application No. 102187-1987, Showa 54-103556
No., Patent Application No. 1982-108507, Special Application No. 1973-123015,
Patent Application No. 124912/1983) etc. are disclosed. Although these catalysts have high activity and can achieve a compact process, the molecular weight distribution of the polymer is narrow and it is not possible to obtain a polymer with a wide molecular weight distribution suitable for extrusion molding. On the other hand, as a catalyst for producing a polymer with a wide molecular weight distribution, for example, a catalyst consisting of an organometallic compound and a solid obtained by reacting a transition metal compound with a reaction product of an organomagnesium complex and a halogenating agent (Japanese Patent Application Laid-Open No. 53-40696 (Japanese Patent Publication No. 146290/1983), Catalyst consisting of a reaction solid of an oxygen-containing organic compound of magnesium, an oxygen-containing organic compound of titanium, an oxygen-containing organic compound of zirconium, and an organic aluminum compound with an organic aluminum halide
−8083, JP-A-54-116077, JP-A-54-
No. 153892), etc., but there are still problems to be improved in the catalytic activity per titanium and zirconium, the powder properties of the polymer, etc. It is also possible to produce low-density polyethylene by copolymerizing ethylene and olefin using a Ziegler catalyst, but in order to use olefin efficiently, a catalyst with good copolymerizability is desirable. Furthermore, problems unique to each polymerization method remain.
For example, in the solution polymerization method, by increasing the polymerization temperature, the heat of polymerization can be easily removed, and the viscosity of the solution is lowered, so that it is possible to increase the solution concentration and increase the production amount. However, as the polymerization temperature increases, the catalyst activity decreases, and it becomes difficult to produce a polymer with a low MI. On the other hand, in suspension polymerization and gas phase polymerization, it is desired to develop a catalyst that provides a polymer with high bulk density and good powder properties. Polyolefin is generally shipped in the form of pellets, but if the powder properties are good, it can be shipped as a powder, and the pelletizing step can be omitted. Furthermore, improvement of the powder properties of the polymer is an important factor for long-term continuous stable operation of suspension polymerization and gas phase polymerization.
In this way, olefin polymerization catalysts not only have high activity, but also the ability to produce polymers with a wide molecular weight distribution, copolymerizability, high-temperature polymerization activity, MI control performance, suspension polymerization, and gas phase polymerization. It is desired to develop a catalyst that has high performance in all aspects, including powder properties for coalescence. As a result of intensive study, the present inventors found that highly active,
The present invention was achieved by discovering a catalyst that produces a polymer with a wide molecular weight distribution and has good powder characteristics in suspension polymerization and gas phase polymerization. That is, the present invention provides a catalyst for ethylene polymerization or ethylene-α-olefin copolymerization consisting of the following catalytic reactants [A] and [B] [A] Reacting (4) and (5) in the presence of the following (3). (1) General formula MαMgR′pXq・Dr (in the formula, M is a metal element from group to group of the periodic table, α, p, q,
r is a number greater than or equal to 0, p+q=mα+2, 0≦
q/ ₍ 〓 ₊₁₎ <2, where m is the valence of M, R' is one or a mixture of two or more hydrocarbon groups having 1 to 20 carbon atoms, and X is a hydrogen atom. or a mixture of one or more negative groups containing oxygen, nitrogen or sulfur atoms; D represents an electron-donating organic compound)
An organomagnesium compound represented by (2) One type or a mixture of two or more types selected from boron, silicon, germanium, tin, phosphorus, antimony, bismuth, zinc halides, hydrogen chloride, or organic halides. (3) Solid components resulting from the reactions of (1) and (2). (4) One or a mixture of two or more selected from organolithium compounds, organomagnesium compounds, organoaluminum compounds, and organozinc compounds. (5) Titanium compound and zirconium compound [B] This relates to one or a mixture of two or more selected from organoaluminum compounds, organomagnesium compounds, and organozinc compounds. When α-olefin is polymerized using the catalyst of the present invention described above, the following surprising effects are achieved. 1 The characteristics of the present invention are suspension polymerization method, solution polymerization method,
It exhibits high activity in any α-olefin polymerization method, which is a gas phase polymerization method, and has sufficient performance to omit the catalyst residue removal step. 2 The catalyst of the present invention is suitable for producing a polymer of α-olefin with a wide molecular weight distribution suitable for extrusion molding. 3. The catalyst of the present invention can efficiently copolymerize two or more types of α-olefins and easily produce a low-density polymer. 4. The catalyst of the present invention enables the production of high molecular weight (that is, low MI) polymers by solution polymerization, particularly at high polymerization temperatures. 5. The catalyst of the present invention produces a polymer with uniform particle size, high bulk density, and good powder properties in suspension polymerization and gas phase polymerization. This results in
This makes it possible to increase the polymer concentration in the polymerization reactor, improve productivity, and facilitate shipment in powder form. The solid catalyst [A] used in the present invention will be explained in detail. First, (1) general formula MαMgR′pXq・Dr (where M,
The organomagnesium compound represented by R', X, D, α, p, q, r are as defined above) will be explained. Although (1) is shown as an organomagnesium complex, it includes all dihydrocarpylmagnesiums and their complexes with other metal compounds. In the above formula, M can be a metal element belonging to Groups 1 to 3 of the periodic table, such as lithium, sodium, potassium, beryllium, calcium, strontium, barium, zinc, boron, aluminum, etc. In particular, lithium , beryllium, zinc, boron and aluminum are preferred.
More preferably, aluminum is used. The ratio α of metal atoms M to magnesium atoms is a number of 0 or more, preferably 0≦α≦1, especially 0.01
A range of ≦α≦0.5 is recommended. The hydrocarbon group represented by R' is an alkyl group having 1 to 20 carbon atoms,
One or a mixture of two or more cycloalkyl groups or allyl groups, such as methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, cyclohexyl, phenyl, benzyl groups, etc. , particularly an alkyl group. X represents one type or a mixture of two or more types of a hydrogen atom or a negative group having an oxygen, nitrogen, or sulfur atom. Preferably, OR ² ,
OSiR ³ R ⁴ R ⁵ , NR ⁶ R ⁷ , SR ⁸ ,

[Formula] (In the formula, R ² to ^{R 11} represent a hydrocarbon group having 1 to 20 carbon atoms, R ³ to ^{R 7} , R ¹⁰
may be a hydrogen atom. ) is used, more preferably an alkoxy group (OR ² )
A siloxy group (OSiR ³ R ⁴ R ⁵ ) is recommended. The relational expression p + q = m α + 2 of the symbols α, p, and q indicates the stoichiometry between the valence of the metal atom and the substituent,
A preferable range of 0≦q/ ₍ 〓 ₊₁₎ <2 indicates that X is 0 or more and less than 2 with respect to the sum of metal atoms. It is preferably used in the range of 0≦q/ ₍ 〓 ₊₁₎ <1.5, more preferably in the range of 0≦q/ ₍ 〓 ₊₁₎ <1. The organomagnesium compound used in the present invention needs to be soluble in a hydrocarbon solvent in order to achieve high activity. Generally, organomagnesiums with α=0 are insoluble in hydrocarbon solvents. but,
A special organomagnesium compound, CH ₃ Mg (n-
C ₃ H ₇ ), CH ₃ Mg (i-C ₃ H ₇ ), C ₂ H ₅ Mg (i-
C ₃ H ₇ ), n-C ₃ H ₇ Mg (i-C ₃ H ₇ ), Mg (i-
_C3H7 ) ₂ , n- _{C4H9Mg ( i} - _C3H7 ) _, n-
C ₄ H ₉ Mg (sec-C ₄ H ₉ ), C ₂ H ₅ Mg (n-C ₄ H ₉ ),
C ₂ H ₅ Mg (n-C ₆ H ₁₃ ), n-C ₄ H ₉ , Mg (n-
C ₈ H ₁₇ ), Mg(C ₂ H ₅ ) _0.5 (n−C ₄ H ₉ )(sec−
C ₄ H ₉ ) _0.5 and the like are soluble in hydrocarbon solvents, and these compounds are preferably used in the present invention. As the electron-donating compound represented by D, an electron-donating organic compound containing oxygen, nitrogen, sulfur or phosphorus atoms is used. These compounds include ethers such as diethyl ether, dibutyl ether, diisoamyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, glycerin trimethyl ether, vinyl methyl ether, tetrahydrofuran, dioxane, crown ether, propylene oxide, and hexamethyl dimethyl ether. Siloxane, symmetrical dihydrotetramethyldisiloxane,
Siloxanes such as pentamethyltrihydrotrisiloxane, cyclic methylhydrotetrasiloxane, methylhydropolysiloxane, dimethylpolysiloxane, phenylhydropolysiloxane, triethylamine, tributylamine, tetramethylethylenediamine, bis(dimethylamino)methane, diaza Tertiary amines such as bicyclooctane,
Nitriles such as acetonitrile, propionitrile, acrylonitrile, benzylnitrile, benzonitrile, amides such as dimethylformamide and hexamethylphosphoramide, pyridine derivatives such as pyridine and methylpyridine, diethyl sulfide, ethylpropylsulfide , thioethers such as propyl sulfide and ethylene sulfide, sulfoxides such as dimethyl sulfoxide, diethyl sulfoxide, dibutyl sulfoxide,
These include phosphines such as triethylphosphine and triphenylphosphine. Preferably ethers, siloxanes or amines are used. r is the electron donating organic compound D is M or
It represents the amount coordinated to Mg, and is a number of 0 or more,
It is preferably used in a range of 10 or less, more preferably 2 or less. In order to exhibit high activity performance at high temperatures, it is preferable to contain X or D. These magnesium compounds have the general formula
R′MgY, R′ ₂ Mg (Y is a halogen atom, R′ is the meaning described above), or a mixture thereof, and the general formula MR′ _n , MR′ _a X _b Y _c , MR′ _n
D _r , MR′ _a X _b Y _c D _r (where M, R′, X, Y, D,
m and r have the above-mentioned meanings and have the relationship a+b+c=m) or an electron-donating organic compound represented by D, such as hexane, heptane, octane, cyclohexane, benzene, toluene, etc. Synthesized by reacting in a hydrocarbon solvent between 0 and 150°C, and if necessary, subsequently reacting this with an electron-donating organic compound or alcohol, siloxane, amine, imine, thiol, or dithio compound. . Next, (2) one or a mixture of two or more selected from halides of boron, silicon, germanium, tin, phosphorus, antimony, bismuth, zinc, or hydrogen chloride will be explained. A halide is a compound having at least one halogen atom, and chloride is preferred. Specific examples of these compounds include trichlorboron, ethylboron dichloride, butylboron dichloride,
Boron halides such as phenylboron dichloride, diethylboron chloride, dibutylboron chloride, diphenylboron chloride, ethoxyboron dichloride, tripromboron, tetrachlorosilane, trichlorosilane, methylchlorosilane, methyldichlorosilane, methyltrichlor Silane, dimethylchlorosilane, dimethyldichlorosilane, trimethylchlorosilane, ethyldichlorosilane, ethyltrichlorosilane, diethylchlorosilane, diethyldichlorosilane, triethylchlorosilane, vinyltrichlorosilane, vinyldichlorosilane, propyltrichlorosilane,
Propyldichlorosilane, allyltrichlorosilane, butyltrichlorosilane, butyldichlorosilane, octyldichlorosilane, decyldichlorosilane, isobutyltrichlorosilane, sec-
Butyltrichlorosilane, tert-butyltrichlorosilane, sym-tetramethyldichlorodisilane, pentachlordisylmethylene, hexachlordisylmethylene, hexachlorocyclotrisylmethylene, phenyltrichlorosilane, phenyldichlorosilane, benzyltrichlor Silane, silicon halides such as ethoxytrichlorosilane, diethoxydichlorosilane, butoxytrichlorosilane, octoxytrichlorosilane, tetraglomsilane, tetrachlorogermane, methyltrichlorogermane, dimethyldichlorogermane, trimethylchlorogermane, ethyltrichlorogermane , germanium halides such as butyltrichlorogermane, ethoxytrichlorogermane, tin halides such as tetrachlortin, methyltrichlortin, diethyldichlortin, dibutoxydichlorotin, trioctylchlortin, tetrabromtin, and phosphorus trichloride. , phosphorus tribromide, phosphorus pentachloride, phosphorus halides such as ethyldichlorphosphine, propyldichlorphosphine, methyldichlorstibine, trimethylantimony dichloride,
Antimony halides such as tripropylantimony dichloride, bismuth halides such as methyldichlorbismuthine, ethyldichlorbismuthine, butyldichlorbismuthine, dimethylchlorbismuthin, zinc halides such as zinc chloride, ethylzinc chloride, butylzinc chloride, etc. It is. In order to obtain a polymer with good powder properties, preferably,
Chlorides of boron, tin, silicon, and germanium are used, and silicon chloride is more preferably used. As component (4), organic metal compounds or organic complex compounds of lithium, magnesium, aluminum, and zinc are used, and specifically, organic lithium compounds such as ethyllithium and butyllithium,
M〓M _g R′ _p X _q・D _r (in the formula M・R′・X・D・α・p・
q and r have the above-mentioned meanings), triethylaluminum, tributylaluminum, trioctylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, dibutylaluminum chloride, decylaluminum dichloride, diethylaluminium Examples include organic aluminum compounds such as ethoxide, dibutylaluminum ethoxide, ethyl ethoxyaluminum chloride, trimethylsiloxyethylaluminum chloride, tetraisobutylaluminoxane, and isoprenylaluminum, and organic zinc compounds such as diethylzinc and dibutylzinc. In order to achieve the effects of the present invention, organoaluminum compounds are preferred, and more preferably trialkylaluminiums, alkylaluminum halides, or mixtures thereof are recommended. (5) Titanium compounds and zirconium compounds will be explained. Titanium compounds include titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, ethoxytitanium trichloride, propoxytitanium trichloride, butoxytitanium trichloride, octoxytitanium trichloride, diethoxytitanium dichloride, and diproboxytitanium dichloride. , dibutoxytitanium dichloride, triethoxytitanium chloride, tripropoxytitanium chloride, tributoxytitanium chloride, phenoxytitanium trichloride, benzoyltitanium trichloride, dicyclopentadienyltitanium dichloride, tetraisopropoxytitanium, tetrabutoxytitanium, Examples include halides, alkoxy halides, alkoxides, siloxy halides, siloxide compounds, aromatic ring complex compounds, and chelate compounds such as bis(triphenylsiloxy) titanium dichloride, dicyclopentadienyl dichloride, and titanium acetylacetonate. Examples of zirconium compounds include zirconium tetrachloride, zirconium tetrabromide, ethoxytrichlorzircon, butoxytrichlorzircon, diethoxydichlorzircon, dibutoxydichlorzircon, ethoxytrichlorzircon, butoxytrichlorzircon, tetraethoxyzircon, tetrabutoxyzircon, Examples include halides such as zirconium acetylacetonate, alkoxy halides, alkoxides, and chelate compounds. Both the titanium compound and the zirconium compound are preferably tetravalent compounds. Also,
In order to smoothly proceed with catalyst synthesis, it is desirable to be soluble in a solvent. As a solvent, components (3) and (4),
Hydrocarbon compounds used as reaction solvents in (5) are suitable, but alcohols, ethers, etc. are also suitable as long as they are used in small proportions relative to the total amount of reaction solvents in (3), (4), and (5). Available. In order to obtain a polymer with a wide molecular weight distribution, the molar ratio of titanium and zirconium is determined by weight, with Zr/Ti being 10 to 0.2, preferably Zr/Ti being 4.
~0.6 used. (6) Examples of the solid inorganic oxide include silica, alumina, silica-alumina, magnesia, thoria, zirconia, or a mixture of two or more thereof. In particular silica or silica-alumina is used. The specific surface area of the solid inorganic oxide is preferably 20 m ² /g or more, more preferably 100 m ² /g
Above, the particle size is 0.01~500μ, preferably 0.1~
100μ is recommended. (6) It is recommended to use the solid inorganic oxide after drying it at 200°C to 1200°C, preferably 300°C to 900°C under a stream of inert gas or under reduced pressure to obtain stable reproducibility. By using a solid inorganic oxide, the particle size of the polymer can be easily controlled, and not only titanium and zirconium but also magnesium and halogen in the polymer can be reduced. (7) As the electron-donating organic compound, an electron-donating organic compound containing oxygen, nitrogen, sulfur, or phosphorus atoms is used. These compounds include ethers such as diethyl ether, dibutyl ether, diisoamyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, glycerin trimethyl ether, vinyl methyl ether, tetrahydrofuran, dioxane, crown ether, propylene oxide, and hexamethyl dimethyl ether. Siloxane, symmetrical dihydrotetramethyldisiloxane, pentamethyltrihydrotrisiloxane, cyclic methylhydrotetrasiloxane, methylhydropolysiloxane, dimethylpolysiloxane, phenylhydropolysiloxane and other siloxanes, triethylamine, tributylamine, tetramethylethylenediamine, Tertiary amines such as bis(dimethylamino)methane and diazabicyclooctane, nitriles such as acetonitrile, propionitrile, acrylonitrile, benzylnitrile, and benzonitrile, amides such as dimethylformamide and hexamethylphosphoramide, pyridine , pyridine derivatives such as methylpyridine, diethyl sulfide, ethylpropyl sulfide, propyl sulfide,
Thioethers such as ethylene sulfide, sulfoxides such as dimethyl sulfoxide, diethyl sulfoxide, dibutyl sulfoxide, phosphines such as triethylphosphine, triphenylphosphine, ethyl benzoate, ethyl p-toluate, ethyl thiophenecarboxylate. and organic acid esters. Preferably ether, siloxane,
Amines or organic acid esters are used. The copolymerization performance is further improved by the action of these electron donors. Next, a method for synthesizing component (3) will be explained. Reactions (1) and (2) can be carried out using a simultaneous addition method in which two components are simultaneously introduced into the reaction zone and reacted, or one component is charged into the reaction zone in advance and the remaining component is introduced while reacting. Make it react. Any so-called forward (reverse) addition method is possible. The reaction temperature is not particularly limited, but in view of the reaction progress, it is preferably carried out at -50 to 150°C, particularly preferably 0 to 100°C. There is no particular restriction on the reaction ratio of the two components, but preferably the reaction ratio of the two components is
The recommended amount of component (2) is 0.01 to 100 mol, particularly preferably 0.2 to 10 mol, per 1 mol of (1). component
For the number of moles in (1), a value calculated as the sum of metal atoms M and magnesium atoms is used. for example,
AlMg(C ₂ H ₅ ) ₃ (n-C ₄ H ₉ ) ₂ has a molecular weight of 252 g and 2 mol. Solid component (3) is produced by the reaction of (1) and (2), but in order to control the reaction with (4) and (5), (4) is separated by decantation or filtration. It is important to proceed with reaction (5). When synthesizing component (3) by reacting components (1), (2) and (6), the reaction of (1) and (2) is carried out under the above-mentioned conditions in the presence of (6). There is no particular restriction on the reaction ratio, but 0.05 mmol to 100 m of component (1) per 1 g of component (6).
mol, preferably in the range of 0.1 to 50 mmol. Component (2) is used in a molar amount within the above-mentioned range relative to component (1). Component (7) is, for 1 mol of Mg atom of solid component (3),
It is used in an amount of 0.01 to 100 mol, preferably 0.1 to 20 mol. The reaction takes place in the range of 0 to 100℃, when component (7)
It is carried out at a concentration of 1 mol/or less. Next, the reaction between component (3), component (4), a titanium compound (hereinafter referred to as component (5-1)), and a zirconium compound (hereinafter referred to as component (5-2)) will be explained. The reaction can be carried out by simultaneously introducing components (4), (5-1), and (5-2) into a suspension of component (3) in a hydrocarbon solvent, or by simultaneously introducing components (4), (5-1), and ( The three components 5-2) may be sequentially introduced in any order and the reaction may be carried out. A preferred method is to introduce components (5-1) and (5-2) into a suspension of component (3) in a hydrocarbon solvent, and then introduce component (4).
The recommended method is to prepare 2) and then introduce components (4) and (5-1) in this order. Furthermore, components (4) and (5
After reacting -2), component (4) and component (5-1) different from those used in the reaction with component (5-2)
It is also possible to introduce and carry out the reaction. The reaction temperature and time are not particularly limited, but from the viewpoint of reaction progress, preferably -50 to 150°C, particularly preferably 0 to 150°C.
It is carried out at a temperature range of 100° C. for a period of 1 minute to 24 hours. In order to achieve the effects of the present invention, component (3),
The ratio of the four components (4), (5-1), and (5-2) is important. For 1 mol of magnesium of component (3),
Components (5-1) and (5-2) are Ti + Zr
0.35mol~0.001mol, preferably 0.25mol~
A range of 0.005 mol, particularly preferably 0.1 mol to 0.01 mol is required. Furthermore, component (5-1) is preferably 0.23 mol or less per 1 mol of magnesium.
It is used in the range of 0.2mol to 0.0005mol. Ingredients (4)
The usage amount of Ti+ is determined by the molar ratio with component (5).
The amount of component (4) is in the range of 0.1 mol to 100 mol, preferably 0.5 mol to 50 mol, per 1 mol of Zr. After completion of the reaction, the solid catalyst [A] can be directly subjected to polymerization, or can be isolated by filtration or washed by decantation before being subjected to polymerization. As the catalyst component [B], Al(C ₂ H ₅ ) ₃ , Al
( _C3H7 ) ₃ , Al _{( C4H9} ) ₃ , Al _{( C5H11} ) ₃ , _Al
Trialkylaluminum such as (C ₆ H ₁₃ ) ₃ , Al (C ₈ H ₁₇ ) ₃ , Al (C ₁₀ H ₂₁ ) ₃ , Al (C ₂ H ₅ ) ₂ H, Al (i-
Alkylaluminum hydrides _such as _C4H9 ) _2H , Al( _C2H5 ) _{2Cl ,} Al( _C2H5 ) _Cl2 , Al ₍ i-
Alkylaluminum halides such as C ₄ H ₉ )Cl ₂ , Al(C ₂ H ₅ ) ₂ Br, Al(C ₂ H ₅ ) ₂ (OC ₂ H ₅ ), Al(i-
Alkoxyalkyl aluminum such as C ₄ H ₉ ) ₂ (OC ₄ H ₉ ), Al(C ₂ H ₅ ) ₂ (OSiHCH ₃ C ₂ H ₅ ), Al(i-
Siloxyalkyl aluminum, isobrenyl aluminum, such as C ₄ H ₉ ) ₂ (OSi(CH ₃ ) ₂ i−C ₄ H ₉ ),
Organoaluminum compounds such as reaction products of alkyl aluminum such as myrcenyl aluminum and conjugated diene, Zn(C ₂ H ₅ ) ₂ , Zn(C ₄ H ₉ ) ₂ , Zn
_{( C6H13} ) ₂ , Zn( _C8H17 ) ₂ , Zn _{( C2H5} )( _n-
Organozinc compounds such as C ₃ H ₇ ), Zn(C ₆ H ₅ ) ₂ , Zn(C ₃ H・)(OC ₄ H ₉ ), with the general formula M〓M _g R′ _p X _q・D _r (formula During,
M, R', X, D, α, p, q, r have the above meanings)
Organomagnesium compounds represented by the following and mixtures thereof are used. To achieve high activity, trialkylaluminum is preferred. Catalyst components [A] and [B] may be added into the polymerization system under polymerization conditions, or may be combined in advance prior to polymerization. The ratio of both components to be combined is defined by the molar ratio of Ti+Zr in the [A] component to the [B] component, preferably [B]/(Ti+Zr) is 3/1 to 1000/1, more preferably 5 A range of /1 to 500/1 is used. The catalyst of the present invention comprises catalyst components [A] and [B]
By using [C], a polymer with a wide molecular weight distribution can be obtained, but by using [C] halogenated hydrocarbon as the third component, a polymer with a wider molecular weight distribution can be obtained. Examples of halogenated hydrocarbons include dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,2-
Trichloroethane, 1,1,2,2-tetrachloroethane, propyl chloride, 1,2-dichloropropane, 1,2,3-trichloropropane, butyl chloride, 1,2-dichlorobutane, 1,
Examples include 2,3,4-tetrachlorobutane, hexyl chloride, phenyl chloride, benzyl chloride, bromoform, 1,2-dichlorobutane, and methyl iodide. Chloride is stable and easy to use. Preferably, a compound in which the ratio of halogen atoms to carbon atoms is 1 or more is used. The amount used is in the range of 0.01 mol to 100 mol, preferably 0.1 mol to 10 mol, per 1 mol of catalyst component [B]. As the method for polymerizing olefin using the catalyst of the present invention, suspension polymerization or solution polymerization in the presence of a solvent, or gas phase polymerization in the absence of a solvent can be employed. Suspension polymerization uses polymerization catalysts such as propane, butane, isobutane, pentane,
Aliphatic hydrocarbons such as isopentane, hexane, and heptane, aromatic hydrocarbons such as benzene and toluene, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane are introduced into the reactor, and a catalyst is introduced into the reactor to react with the olefin under an inert atmosphere. 1~50Kg/ ^cm2
The polymerization can be accelerated at temperatures between 30°C and 110°C. In order to obtain a low-density ethylene copolymer in a good powder state, it is preferable to use an aliphatic hydrocarbon having 6 or less carbon atoms as a solvent. In solution polymerization, a catalyst is introduced into a reactor together with a polymerization solvent as described for suspension polymerization, and olefin is added at a rate of 1 to 400 kg/cm 2 , preferably 10 to 400 kg/cm ² under an inert atmosphere.
The polymerization can be carried out at a temperature of 120 to 350°C, more preferably 150 to 320°C by injecting at 250 kg/cm ² . In gas phase polymerization, methods such as mixing using a fluidized bed, moving bed, or stirrer are used to ensure good contact between the olefin and the catalyst, and the temperature is 30°C to 120°C at a pressure of 1 to 50 kg/ ^cm2 . Polymerization can be carried out under temperature conditions. The polymerization may be carried out in a single-stage polymerization using one reaction zone, or it is also possible to carry out a so-called multi-stage polymerization using a plurality of reaction zones. This polymerization method is 1
Step polymerization also produces polymers with a wide molecular weight distribution, but
It is also possible to produce a polymer with a broader molecular weight distribution by multistage polymerization. In addition, to control the molecular weight, you can change the temperature of the reactor or
Alternatively, it is also possible to add hydrogen or an organic compound that is likely to undergo chain transfer. Low-density polyethylene can be produced by copolymerizing ethylene and other olefins; other olefins include propylene, 1-butene, 1-
α-olefins such as pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, and 4-methyl-1-pentene. In the suspension polymerization method and the gas phase polymerization method, in order to obtain low density polyethylene having good powder properties, copolymerization can be carried out after prepolymerizing a small amount of ethylene. Polymers containing many double bonds in the main chain or side chains can also be produced by carrying out polymerization in the presence of a small amount of conjugated or non-conjugated diene. Examples of the present invention are shown below, but the present invention is not limited to these examples in any way. In these examples, MI stands for melt index, and the temperature is determined according to ASTM D-1238.
Measured under the conditions of 190°C and a load of 2.16 kg. FR is the value measured at a temperature of 190℃ and a load of 21.6Kg.
It means the quotient divided by MI, which is 1 of the scale of molecular weight distribution.
The lower the value, the narrower the molecular weight distribution. Catalytic activity is expressed in kg of polymer produced per gram of Ti+Zr. Example 1 (] Synthesis of organomagnesium compound (1) 5 g of magnesium powder was added to a 200 ml flask that had been purged with nitrogen. 30 ml of n-octane containing 2 mmol of butoxyaluminum dichloride was added, and the temperature was raised to 100°C. n- butyl chloride
70 ml of n-octane containing 100 mmol of ethyl bromide and 100 mmol of ethyl bromide were added dropwise over 2 hours while stirring at 100°C, and after the addition was completed, the mixture was further stirred for 1 hour. When the solid matter was filtered out and the filtrate was analyzed, Al _0.02
It had a composition of Mg(C ₂ H ₅ ) _1.02 (n-C ₄ H ₉ ) _1.02 (C _o C ₄ H ₉ ) _0.02 , and the concentration of the compound was 0.87 mol/. () Synthesis of solid catalyst [A] Oxygen and moisture inside a 250 ml flask equipped with a dropping funnel and a water-cooled reflux condenser were removed by nitrogen substitution, and a heptane solution of 1 mol of trichlorosilane was added under a nitrogen atmosphere. 25 ml and 25 ml of heptane were charged and the temperature was raised to 70°C. next,
25 ml of the above component (1) and 25 ml of heptane were weighed into a dropping funnel, and added dropwise to the mixture over 2 hours while stirring at 70°C. As a result, the reaction solution became a white suspension. The mixture was cooled to room temperature and allowed to stand, the supernatant water was removed by decantation, the mixture was washed twice with 50 ml of heptane, and then heptane was added to bring the volume to 100 ml.
Add 0.53 mmol of tetrabutoxytitanium to this reaction solution.
After introducing 1.06 mmol of tetrabutoxyzircone and 10.5 mmol of ethylaluminum dichloride and carrying out a reaction at 60°C for 2 hours, the solid catalyst was filtered off, washed and dried. Ti in the solid catalyst is
The content was 1.1wt%, and Zr was 4.2%. () Polymerization Polymerization-1 20 mg of the solid catalyst [A] synthesized in () and 800 ml of hexane obtained by dehydrating and degassing 0.25 mmol of triisobutylaluminum were introduced into a 1.5 autoclave whose interior had been dehydrated and degassed, and the internal temperature of the autoclave was adjusted to 80°C. The temperature rose to . 9.6Kg of hydrogen/
It was pressurized to a pressure of cm ² and then ethylene was introduced to give a total pressure of 20 Kg/cm ² gauge. Polymerization was carried out for 1 hour while maintaining a gauge pressure of 20 kg/cm ² by replenishing ethylene to obtain 109 g of powder. Catalytic activity is 103Kg/g (Ti + Zr), MI is 0.21, FR is
It was 83. Also, the bulk density of the polymer powder is 0.37.
The powder content was 65 wt% or more with a particle diameter of 105 μ to 149 μ in g/cm ² . Polymerization-2 20 mg of the solid catalyst [A] synthesized in () and 0.1 mmol of triethylaluminum were introduced into a 1.5 autoclave whose interior had been dehydrated and degassed together with 800 ml of cyclohexane. Next, after charging 25 mmol of hydrogen and 800 mmol of 1-octene, the autoclave was heated to 160°C.
Ethylene was introduced to bring the total pressure to a gauge pressure of 33 Kg/cm ² . 33Kg/cm ² by supplementing with ethylene
Polymerization was carried out for 20 minutes while maintaining the gauge pressure of 40 g of polymer. Catalytic activity is 235Kg/g (Ti+
Zr), MI was 0.89, FR was 58, and density was 0.927. Polymerization-3 Polymerization was carried out in a gas phase using a 50-volume stainless steel fluidized bed autoclave. In an autoclave adjusted to 80℃, add 100 mg of the solid catalyst [A] synthesized in () and 20 m of triethylaluminum.
mol, and the molar ratio of ethylene:hydrogen is 1:
1 at a gauge pressure of 20 Kg/cm ² while introducing a gas of composition 0.20 into the autoclave at a rate of 15 cm/s.
Powder 1100 with a bulk density of 0.37g/ ^cm3 after polymerization for a period of time
I got g. Catalytic activity is 207Kg/g (Ti + Zr),
MI was 0.32 and FR was 71. Examples 2 to 10 Capacity with dropping funnel and water-cooled reflux condenser installed
Oxygen and moisture inside a 250 ml flask were removed by nitrogen substitution, and 50 ml of heptane containing 30 mmol of trichlorosilane was charged in a nitrogen atmosphere at 60°C.
The temperature rose to . Next, Al _0.1 Mg(C ₂ H ₅ ) _1.7 (n-
50 ml of a heptane solution containing 25 mmol of C ₈ H ₁₇ ) _0.5 (On-C ₄ H ₉ ) _0.1 was weighed into a dropping funnel, and added dropwise at 60° C. over 1 hour with stirring. As a result, the reaction solution became a white suspension. The mixture was cooled to room temperature and allowed to stand, the supernatant liquid was removed by decantation, and the mixture was further washed three times with 50 ml of heptane, and then heptane was added to make a 100 ml suspension. Component (4) and components (5-1) and (5-2) shown in Table 1 were added to this reaction solution, and the reaction was carried out at 60° C. for 4 hours. The supernatant was removed by decantation, and heptane was added to form a suspension, which was used for polymerization. The polymerization was carried out according to the method of Polymerization-1 in Example 1 using the solid catalyst [A] synthesized in this way at 0.02 mmol per (Ti + Zr) and the solid components [B] and [C] shown in Table 2. Ethylene polymerization was carried out and the results shown in Table 2 were obtained.

【table】

【table】

[Table] Example 11 Oxygen and moisture inside a 250 ml flask equipped with two dropping funnels and a water-cooled reflux condenser were removed by nitrogen substitution, and hexane was added under a nitrogen atmosphere.
I prepared 40ml. Al _0.2 Mg in each dropping funnel
(C ₂ H ₅ ) _0.4 (n-C ₅ H ₁₁ ) _1.0 (OSi(CH ₃ ) ₃ ) _1.2 35m
mol of hexane and 30 ml of hexane containing 30 mmol of methyldichlorosilane were weighed out. After raising the internal temperature of the flask to 60°C, the two components were simultaneously introduced into the flask and the reaction was carried out over a period of 2 hours. After the reaction was completed, the produced solid was washed by decantation and made into a suspension in 200 ml of hexane. Add 1.22 mmol of tetrabutoxyzircon and ethylaluminum dichloride to this reaction solution.
After introducing 11.6 mmol and carrying out the reaction at 65°C for 3 hours, 0.24 mmol of titanium tetrachloride was added, and further 65 mmol of titanium tetrachloride was introduced.
The reaction was carried out at ℃ for 1 hour. Solids were filtered out from this reaction solution, washed with hexane, and dried to obtain a solid catalyst. This solid catalyst was mixed with 0.02 mmol per titanium and zirconium atom, and trioctylaluminum.
Polymerization was carried out under the same conditions as in Example 1, Polymerization-1, except that 0.5 mmol was used. As a result, the catalyst activity was 102 Kg/g (Ti+Zr), the MI was 0.12, the FR was 68, and the bulk density of the polymer was 0.37. Example 12 Al _0.3 Mg (n-C ₄ H ₉ ) _1.0 (n-C ₈ H ₁₇ ) _1.6 (On-
C ₄ H ₉ ) _0.6 15 mmol and tetrachlorosilane 30 mmol
was reacted under the same conditions as in Example 11 and washed. Next, 0.1 mmol of titanium tetrachloride and mmol of ethylaluminum dichloride were added, and after reacting at 50°C for 1 hour, 0.3 mmol of tetrabutoxyzirconate was added.
After introducing 3 mmol of ethylaluminum dichloride and carrying out the reaction at 50° C. for further 2 hours, the solid catalyst was filtered off and dried. Polymerization was carried out in the same manner as in Example 1, Polymerization-1, except that 0.02 mmol of this solid catalyst and 0.5 mmol of trioctylaluminum were used per titanium and zirconium atom.
As a result, the catalyst activity was 175Kg/g (Ti + Zr), MI
was 0.36, FR was 66, and the bulk density of the polymer was 0.37. Example 13 Mg(n-C ₆ H ₁₃ ) ₂ [O(n-C ₄ H ₉ ) ₂ ] _1.5 90 mmol,
tin tetrachloride 50 mmol, titanium tetrachloride 11.3 mmol,
Zirconium tetrachloride dissolved in dibutyl ether 11.3
mmol and triisobutylaluminum 30m
mol reaction was carried out in the same manner as in Example 11 to obtain a solid catalyst. Homopolymerization of ethylene was carried out under the same conditions as in Polymerization-2 of Example 1, except that 0.01 mmol of this solid catalyst and 0.8 mmol of triethylaluminum were used per titanium and zirconium atom, and only 50 mmol of hydrogen was charged. As a result, the catalyst activity was 86 Kg/g (Ti+Zr), MI was 0.12, and FR was 59. Example 14 B _0.6 Mg (n-C ₄ H ₉ ) _3.1 (N (C ₂ H ₅ ) ₂ ) _0.7 20 mmol,
Germanium tetrachloride 80 mmol, titanium tetrachloride 2.25
mmol, 1.5 mmol of zirconium tetrachloride and 11.3 trioctylaluminum dissolved in n-butanol
A reaction of mmol was carried out in the same manner as in Example 11 to obtain a solid catalyst. Polymerization was carried out under the same conditions as in Polymerization-2 of Example 1, except that 0.02 mmol of this solid catalyst was used per titanium and zirconium atom. As a result, the catalyst activity was 79Kg/g (Ti + Zr), and the MI was
0.43, FR was 56, and density was 0.931. Example 15 L _i0.05 Mg (C ₂ H ₅ ) _1.05 (n-C ₃ H ₇ ) _1.0 30 mmol, boron trichloride 40 mmol, tetrabutoxytitanium 0.42
2.52 mmol of zirconium tetrachloride and 29.4 mmol of ethylaluminum sesquichloride dissolved in dibutyl ether were reacted in the same manner as in Example 11 to obtain a solid catalyst. Polymerization was carried out under the same conditions as in Example 1, Polymerization-1, except that 0.02 mmol of this solid catalyst was used per titanium and zirconium atom. As a result, the catalytic activity was 89Kg/g (Ti+
Zr) MI was 0.32, FR was 76, and bulk height was 0.32 g/cm ³ . Example 16 Al _0.02 Mg (C ₂ H ₅ ) _1.0 (n-C ₄ H ₉ ) _1.0
(OCH ₂ CH ₂ O) _0.03 30 mmol and trichlorosilane 35
mmol was reacted under the same conditions as in Example 11 and washed. Next, 1.32 mmol of tetrabutoxyzircon
After adding 13.5 mmol of ethylaluminum dichloride and reacting at 65°C for 2 hours, the supernatant liquid was removed by decantation, and hexane was added to make the liquid volume the same as before decantation. Add 0.44 mmol of titanium tetrachloride and diethyl aluminum ethoxide to this reaction solution.
After adding 0.45 mmol and carrying out the reaction at 40°C for 1 hour, the solid catalyst was filtered off and dried. Polymerization was carried out under the same conditions as in Polymerization-1 of Example 1, except that 0.02 mmol of this solid catalyst was used per titanium and zirconium atom. As a result, the catalyst activity was 186Kg/g
(Ti+Zr), MI is 0.22, FR is 85, bulk density is 0.39
g/ ^cm2 . Examples 17-19 Capacity with dropping funnel and water-cooled reflux condenser installed
Oxygen and moisture inside a 500 ml flask were removed by nitrogen substitution, and decane containing the solid inorganic oxide shown in Table 3 and 2 mmol of trichlorovinylsilane was added.
200 mmol was added and the temperature was raised to 60°C. Next, Al _0.01 Mg(n-C ₆ H ₁₃ ) _2.03 [O(i-
100 ml of decane containing ₃ mmol of C ₅ H ₁₁ ) was added dropwise at this temperature over a period of 1 hour. Filter off the solid components and make a suspension in 200ml of decane, containing 0.05mmol of tetrabutoxytitanium and 0.15mmol of tetrabutoxyzircone.
mmol and 1.0 m of ethylaluminum dichloride
mol was added dropwise and the reaction was carried out at 150℃ for 3 hours.
It was filtered and dried to obtain a solid catalyst. Gas phase polymerization was carried out under the conditions of Polymerization-3 of Example 1, except that 0.1 mmol of this solid catalyst and 20 mmol of trioctylaluminum were used per titanium and zirconium atom, and the results shown in Table 3 were obtained.

[Table] Example 20 Capacity with dropping funnel and water-cooled reflux condenser installed
Oxygen and moisture inside the 500 ml flask were removed by nitrogen substitution, and Al _0.15 Mg(C ₂ H ₅ ) _1.0 (n-C ₄ H ₉ ) _1.0 (n-
50 ml of hexane containing 40 mmol of C ₁₀ H ₂₁ ) _0.45 was charged, and the temperature was raised to 40°C. Next, weigh out 50 ml of hexane containing 60 mmol of trichlorosilane, and
The mixture was added dropwise at ℃ for 1 hour while stirring. In this reaction solution,
100 ml of hexane with 3 mmol of ethyl benzoate
was added thereto, and the reaction was carried out under heating under reflux for 2 hours. After cooling to room temperature and washing by decantation, hexane was added to make 200 ml. To this was added 1.60 mmol of tetrabutoxyzircon and 6.5 mmol of isobutylaluminum dichloride, and the reaction was carried out at 60°C for 1 hour. Then, 0.5 mmol of titanium tetrachloride was added and the reaction was carried out at 60°C for 2 hours. Hexane was added to the mixture to make it 350 ml, then ethylene containing 5 mol% of hydrogen was introduced, 0.7 mol of ethylene was prepolymerized at 60°C, and the solid was isolated. This solid was introduced into a fluidized bed autoclave at 0.1 mmol per titanium and zirconium atom and 10 mmol triethylaluminum per atom, except that a gas with a composition of ethylene, 1-butene:hydrogen in a molar ratio of 1:0.3:0.1 was used. Polymerization was carried out under the same conditions as in Polymerization-3 of Example 1 to obtain a powder having a bulk density of 0.35 g/cm ³ .
Catalytic activity is 186Kg/g (Ti+Zr), MI is 3.5, FR
was 62, and the density was 0.922.

[Brief explanation of drawings]

FIG. 1 is a flow sheet diagram showing the preparation process of the catalyst of the present invention.

Claims (1)

[Scope of Claims] 1. A catalyst for ethylene polymerization or ethylene-α-olefin copolymerization comprising the following catalytic reactants [A] and [B] [A] In the presence of (3) shown below, (4) and ( 5) (1) General formula MαMgR′pX′q・Dr (where M is a metal element from group to group of the periodic table, α, p,
q and r are numbers greater than or equal to 0, p+q=mα+2,
0≦q/(α+1)<2, m is the valence of M, R' is one type or a mixture of two or more types of hydrocarbon groups having 1 to 20 carbon atoms,
X' is a hydrogen atom or one or two negative groups containing oxygen, nitrogen or sulfur atoms.
(2) a halogen compound of boron, silicon, germanium, tin, phosphorus, antimony, bismuth, zinc or hydrogen chloride; (3) Solid component resulting from the reaction of (1) and (2) (4) One or more selected from organolithium compounds, organomagnesium compounds, organoaluminum compounds, and organozinc compounds (5) Titanium compound and zirconium compound [B] One or more mixtures selected from organoaluminum compounds, organomagnesium compounds, and organozinc compounds. 2 After separating the solid component (3) from the reaction solution, this (3)
The catalyst according to claim 1, characterized in that (4) and (5) are reacted in the presence of. 3 Solid catalyst [A] in the presence of (3) (4) and (5) 0.35≧
The catalyst according to claim 1, characterized in that the reaction is carried out under the conditions of (Ti+Zr)/Mg≧0.001. 4 Catalyst for ethylene polymerization or ethylene-α-olefin copolymerization consisting of the catalytic reaction products of [A] and [B] below [A] A solid obtained by reacting (4) and (5) in the presence of (3) below. Catalyst (1) General formula MαMgR′pXq・Dr (in the formula, M is a metal element from group to group of the periodic table, α, p, q,
r is a number greater than or equal to 0, p+q=mα+2, 0≦
It has a relationship of q/(α+1)<2, where m is the valence of M, R' is one type or a mixture of two or more types of hydrocarbon groups having 1 to 20 carbon atoms, and X is a hydrogen atom or oxygen , one or a mixture of two or more negative groups containing nitrogen or sulfur atoms, D represents an electron-donating organic compound) (2) Boron, silicon, germanium, tin, phosphorus , antimony, bismuth, zinc halide, or a mixture of two or more selected from hydrogen chloride (3) Solid component resulting from the reaction of (1), (2), and (6) (4) Organolithium compound, organic One or more mixtures selected from magnesium compounds, organoaluminum compounds, and organozinc compounds (5) Titanium compounds and zirconium compounds (6) Solid inorganic oxides [B] Organoaluminum compounds, organomagnesium compounds, and organozinc compounds One type or a mixture of two or more types selected from compounds. 5 After separating the solid component (3) from the reaction solution, this (3)
The catalyst according to claim 4, characterized in that (4) and (5) are reacted in the presence of. 6 Solid catalyst [A] in the presence of (3) (4) and (5) 0.35≧
The catalyst according to claim 4, characterized in that the reaction is carried out under the conditions of (Ti+Zr)/Mg≧0.001. 7 Catalyst for ethylene polymerization or ethylene-α-olefin copolymerization consisting of the contact reactants of [A] and [B] below [A] A solid obtained by reacting (4) and (5) in the presence of (3) below. Catalyst (1) General formula MαMgR′pXq・Dr (in the formula, M is a metal element from group to group of the periodic table, α, p, q,
r is a number greater than or equal to 0, p+q=mα+2, 0≦
It has a relationship of q/(α+1)<2, where m is the valence of M, R' is one type or a mixture of two or more types of hydrocarbon groups having 1 to 20 carbon atoms, and X is a hydrogen atom or oxygen , one or a mixture of two or more negative groups containing nitrogen or sulfur atoms, D represents an electron-donating organic compound) (2) Boron, silicon, germanium, tin, phosphorus , antimony, bismuth, zinc halide, or a mixture of two or more selected from hydrogen chloride (3) (1) and (2) or the reactants of (1), (2), and (6). (7
)
(4) A mixture of one or more selected from organolithium compounds, organomagnesium compounds, organoaluminum compounds, and organozinc compounds (5) Titanium compounds and zirconium compounds (6) Solid inorganic compounds Oxide (7) Electron-donating organic compound [B] One type or a mixture of two or more types selected from organoaluminum compounds, organomagnesium compounds, and organozinc compounds. 8 After separating the solid component (3) from the reaction solution, this (3)
The catalyst according to claim 7, characterized in that (4) and (5) are reacted in the presence of. 9 Solid catalyst [A] in the presence of (3) (4) and (5) 0.35≧
The catalyst according to claim 7, characterized in that the reaction is carried out under the conditions of (Ti+Zr)/Mg≧0.001.